Devices and methods including polyacetylenes

ABSTRACT

Embodiments described herein relate to compositions, devices, and methods for storage of energy (e.g., electrical energy). In some cases, devices including polyacetylene-containing polymers are provided.

RELATED APPLICATIONS

This Application claims the benefit under 35 U.S.C. § 120 of U.S.application Ser. No. 13/799,152, entitled “DEVICES AND METHODS INCLUDINGPOLYACETYLENES” filed on Mar. 13, 2013, which is herein incorporated byreference in its entirety. Application Ser. No. 13/799,152 claimspriority under 35 U.S.C. § 119(e) to U.S. Provisional Application Ser.No. 61/623,887, entitled “DEVICES AND METHODS INCLUDING POLYACETYLENES”filed on Apr. 13, 2012, which is herein incorporated by reference in itsentirety.

FIELD OF THE INVENTION

Devices for storage of electrical energy are described, as well asrelated methods.

BACKGROUND OF THE INVENTION

Supercapacitors, or electrochemical double-layer capacitors, have beenshown to achieve higher power and longer cycles than other energystorage devices including batteries. Supercapacitors have the potentialto be useful in a wide range of applications including automobiles(e.g., hybrid cars), electronics, and other applications requiring apower source. However, their widespread use has been limited due to theuse of expensive materials and complex handling procedures inmanufacturing.

SUMMARY OF THE INVENTION

Electrical energy storage device are provided, as well as relatedmethods. In some embodiments, the electrical energy storage devicecomprises a first electrode comprising a polymer comprising asubstituted or unsubstituted polyacetylene; a second electrode inelectrochemical communication with the first electrode; a porousseparator material arranged between the first and second electrodes; andan electrolyte in electrochemical communication with the first andsecond electrodes.

Methods for fabricating an electrical energy storage device are alsoprovided. The method may comprise forming a conductive materialcomprising a polymer comprising a substituted or unsubstitutedpolyacetylene on the surface of a substrate.

Methods for storing electrical energy are also provided. The method maycomprise applying an electric field to a device comprising a polymercomprising a substituted or unsubstituted polyacetylene.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1A shows a schematic representation of an energy storage device.

FIG. 1B shows another schematic representation of an energy storagedevice.

FIG. 2 shows the chemical structure of an exemplary unsubstitutedpolyacetylene.

FIG. 3 shows a graph of the voltage of a device including polyacetyleneat various charging states.

FIG. 4 shows a graph of the estimated capacitance of a device includingpolyacetylene on the first discharging curve.

FIG. 5 shows a graph of the integrated energy input and output duringcharging/discharging of a device including polyacetylene.

FIG. 6 shows a schematic representation of a single-cell supercapacitorwith polyacetylene as a positive electrode.

FIG. 7 shows a schematic representation of a multi-cell supercapacitorwith three cells connected in parallel (e.g., a triple stack) withpolyacetylene as a positive electrode.

Other aspects, embodiments and features of the invention will becomeapparent from the following detailed description when considered inconjunction with the accompanying drawings. The accompanying figures areschematic and are not intended to be drawn to scale. For purposes ofclarity, not every component is labeled in every figure, nor is everycomponent of each embodiment of the invention shown where illustrationis not necessary to allow those of ordinary skill in the art tounderstand the invention. All patent applications and patentsincorporated herein by reference are incorporated by reference in theirentirety. In case of conflict, the present specification, includingdefinitions, will control.

DETAILED DESCRIPTION

Embodiments described herein relate to compositions, devices, andmethods for storage of energy (e.g., electrical energy). In some cases,devices including relatively inexpensive and readily availableconductive materials such as polyacetylene-containing polymers aredescribed.

In some embodiments, devices for energy storage are provided. Forexample, the device may be an electrochemical double-layer capacitor,also known as a supercapacitor, supercondenser, electrochemicaldouble-layer capacitor, or ultracapacitor. Typically, the device maystore energy (e.g., electric energy) in an electric field that isestablished by charge separation at an interface between twoelectroactive materials (e.g., electrode and electrolyte). A generalembodiment of an energy storage device can include a first electrode, asecond electrode in electrochemical communication with the firstelectrode, and a separator material (e.g., a porous separator material)arranged between the first and second electrodes. In some embodiments,the first electrode is a cathode and the second electrode is an anode.In some embodiments, the first electrode is an anode and the secondelectrode is a cathode. The device includes an electrolyte or othermobile phase that can dissociate into anions and cations in contact withboth electrodes. The components of the device may be assembled such thatthe electrolyte is arranged between the first and second electrodes.

FIG. 1A shows an illustrative embodiment of a device as describedherein. In the embodiment shown, single-cell device 10 includes a firstelectrode 20, which includes a conductive material 22 in contact with asubstrate 24. A separator material 40 can be formed adjacent toelectrode 20. A second electrode 30 may be arranged in electrochemicalcommunication with the first electrode. For example, as shown in FIG. 1,electrode 30 includes a conductive material 32 in contact with asubstrate 34, conductive material 32 being in contact with a surface ofseparator material 40 that is opposed to the surface of the separatormaterial that is in contact with conductive material 22. An electrolytemay be arranged in contact with both electrode 20 and electrode 30.

In some cases, the device may be a single-cell device. That is, thedevice may include two conductive materials, each formed on differentsubstrates and each conductive material arranged on an opposing side ofa separator material, as shown in FIGS. 1A-B. In some cases, the devicemay be a multi-cell device, for example, as shown in FIG. 7. It shouldbe understood that there are other embodiments in which the number andorientation of the components is varied. In some embodiments, one ormore of the device components can be formed as thin films.

In one embodiment, the first and second electrodes may be placed onopposite surfaces of a substantially planar separator material whereinthe thickness of the separator material determines the distance betweenthe electrodes.

Some embodiments described herein involve the use of a polymercomprising a substituted or unsubstituted polyacetylene, as describedmore fully below. In some cases, the polymer may have a substituted orunsubstituted polyacetylene backbone. In some cases, the polymer may bea copolymer (e.g., random copolymer, block copolymer, etc.), a portionof which may have a substituted or unsubstituted polyacetylene backbone.In some cases, the substituted or unsubstituted polyacetylene polymermay be arranged in a device as an n-type material within a device. Theterm “n-type material” is given its ordinary meaning in the art andrefers to a material that has more negative carriers (electrons) thanpositive carriers (holes). In some cases, the substituted orunsubstituted polyacetylene polymer may be arranged in a device as ap-type material within a device. The term “p-type material” is given itsordinary meaning in the art and refers to a material that has morepositive carriers (holes) than negative carriers (electrons). Those ofordinary skill in the art would be capable of selecting the particularpolyacetylene polymer suitable for use in a particular application. Insome embodiments, the polyacetylene polymer may be selected to includevarious electron-withdrawing groups. Examples of electron-withdrawinggroups include, but are not limited to, fluoro, nitro, cyano, carbonylgroups, sulfonyl, haloaryl (e.g., fluorinated aryls), and haloalkyl(e.g., fluorinated alkyls). In some embodiments, the polyacetylenepolymer may be selected to include various electron-donating groups.Examples of electron-donating groups include, but are not limited to,alkyl, amino, methoxy, and the like.

In some cases, the first electrode includes the polymer comprising thesubstituted or unsubstituted polyacetylene. In some cases, the secondelectrode includes the polymer comprising the substituted orunsubstituted polyacetylene. In some cases, both the first and secondelectrodes include polymers comprising substituted or unsubstitutedpolyacetylenes. In some cases, the polymer may be a polyacetylenepolymer substituted with carbon monoxide groups. The polymer may, insome cases, be arranged as a component of a composite material. Forexample, the composite material may include the polymer comprising thesubstituted or unsubstituted polyacetylene in combination with othercomponents, such as carbon nanotubes, activated carbon, or a metaloxide. In some embodiments, the first electrode includes a polymercomprising a substituted or unsubstituted polyacetylene. In some cases,the first electrode may include a composite material including thepolyacetylene-containing polymer. The first electrode may includeadditional components, such as a charge collector material in physicalcontact with the polymer. For example, the polymer may be formed on thesurface of a substrate comprising the charge collector material, i.e.,the polymer may be formed on a conducting plate substrate. The chargecollector material may be any material capable of facilitating theseparation of charge within a double-layer capacitor. In some cases, thecharge collector material includes a metal and/or a carbon-basedmaterial. Examples of charge collector materials include aluminum,polyacetylene, and glassy carbon.

In some embodiments, the second electrode may include a conductivematerial, including a carbon-based material or a conducting polymer. Forexample, the second electrode may include carbon, activated carbon,graphite, graphene, carbon nanotubes, and/or a conducting polymer suchas polythiophene, polypyrrole, and the like. In some cases, the secondelectrode includes a polymer comprising a substituted or unsubstitutedpolyacetylene as the conductive material, or in addition to theconductive material. In some cases, the second electrode may include acomposite material including the polyacetylene-containing polymer. Thesecond electrode may include additional components, such as a chargecollector material in physical contact with the conductive material. Forexample, the conductive material may be formed on the surface of asubstrate comprising the charge collector material. In some cases, thecharge collector material includes a metal, and/or a carbon-basedmaterial. Examples of charge collector materials include aluminum,polyacetylene, and glassy carbon.

Electrodes described herein, including electrodes which comprisepolyacetylene-containing polymers, may include additional componentsthat may improve the performance, stability and/or other properties ofthe polyacetylene-containing polymer or electrode. For example, theelectrode may include a conductive material in powder form, and mayfurther include a material that binds the powder particles together.Examples of other additives or modifiers include metal salts, metaloxides, polydimethylsiloxane, polystyrene, polypropylene, silicone oil,mineral oil, paraffin, a cellulosic polymer, polybutadiene,polyneopropene, natural rubber, polyimide, or other polymers.

In some cases, at least a portion of an electrode may be fabricated froma mixture containing the polymer comprising the substituted orunsubstituted polyacetylene and a fluid carrier. For example, themixture may be used to form a film or layer containing the substitutedor unsubstituted polyacetylene via a casting method, or other methods.The film or layer may be used as part of an active layer within anelectrode. In some cases, the film or layer may be used as an activelayer in the first electrode. In some cases, the film or layer may beused as an active layer in the second electrode. In some cases, thefilms or layers may have a thickness in the range of about 0.001 mm toabout 100 mm, 0.01 mm to about 100 mm, 0.01 mm to about 10 mm, or, insome cases, about 0.01 mm to about 1 mm.

In some cases, the polyacetylene-containing polymer may be combined withone or more polymers having a different chemical structure, molecularweight, polymer length, polymer morphology, and/or other polymercharacteristic relative to the polyacetylene-containing polymer. Forexample, a polymer blend which includes the polyacetylene-containingpolymer may be utilized in devices described herein. In some cases, thepolyacetylene-containing polymer may be combined with a conductingpolymer. For example, the conducting polymer may be a derivative ofpolyaniline, polyphenylene, polyarylene, poly(bisthiophene phenylene), aladder polymer, poly(arylene vinylene), or poly(arylene ethynylene), anyof which is optionally substituted. In some embodiments, the conductingpolymer is an optionally substituted polythiophene or a copolymerthereof with other conjugated aromatic or alkene units. In someembodiments, the conducting polymer is an optionally substitutedpolypyrrole or a copolymer thereof with other conjugated aromatic oralkene units.

The separator material (e.g., porous separator material) may be anymaterial capable of physically separating the first and secondelectrodes, while also allowing fluids and/or charged species (e.g.,electrolyte) to travel from one electrode to another. The separatormaterial may also be selected to be chemically inert to other componentsof the device, so as to not interfere with device performance (e.g.,charge/discharge of the device). In some cases, the separator materialis paper. In some cases, the separator material comprises a polymer. Forexample, the polymer may include polypropylene, polyethylene, cellulose,a polyarylether, or a fluoropolymer. In some cases, the separatormaterial is a porous separator material.

Any component of the device, or portion thereof, may be porous or mayhave a sufficient number of pores or interstices such that thecomponent, or portion thereof, is readily crossed or permeated by, forexample, a fluid. In some cases, a porous material may improve theperformance of the device by advantageously facilitating the diffusionof charged species to electroactive portions of the device. In somecases, a porous material may improve the performance of the device byincreasing the surface area of an electroactive portion of the device.In some embodiments, a portion of an electrode may be modified to beporous. In some embodiments, at least a portion of the separatormaterial may be selected to be porous.

The device may further include an electrolyte arranged to be inelectrochemical communication with the first and second electrodes. Theelectrolyte can be any material capable of transporting eitherpositively or negatively charged ions or both between two electrodes andshould be chemically compatible with the electrodes. In some cases, theelectrolyte is selected to be capable of supporting high chargestabilization. In some embodiments, the electrolyte comprises a liquid.In one set of embodiment, the electrolyte is an ionic liquid. Otherexamples of electrolytes include ethylene carbonate solutions orpropylene carbonate solutions, either of which include at least one salthaving the formula, [(R)₄N⁺][X⁻], wherein X is (PF₆)⁻, (BF₄)⁻,(SO₃R^(a))⁻, (R^(a)SO₂—N—SO₂R^(a))⁻, CF₃COO⁻, (CF₃)₃CO⁻ or (CF₃)₂CHO)⁻,wherein R is alkyl and R^(a) is alkyl, aryl, fluorinated alkyl, orfluorinated aryl. In some embodiments the nitrogen of the ammonium ionmay be part of a ring system. In another embodiment, the electrolyte mayinclude a quaternary nitrogen species in which the nitrogen has an sp²electronic configuration, such as an imidazolium cation.

In some embodiments, the electrolyte may selected to be substantiallyfree of metal-containing species (e.g., metals or metal ions), or mayinclude less than about 1%, less than about 0.1%, less than about 0.01%,less than about 0.001%, or less than about 0.0001% of metals and/ormetal ions, based on the total amount of electrolyte. In someembodiments, the electrolyte may be selected to be substantially free oflithium-containing species or lithium ion-containing species. In someembodiments, the electrolyte does not include metal-containing species.

Methods for storing electrical energy using any of the devices describedherein are also provided. For example, the method may involveapplication of an electric field to a device as described herein. Insome embodiments, the device may exhibit a specific capacitance of about50 Farad/g, about 100 Farad/g, about 150 Farad/g, about 200 Farad/g(e.g., about 220 Farad/g), about 300 Farad/g, about 400 Farad/g, or, insome cases, about 500 Farad/g. For example, the device may exhibit aspecific capacitance in the range of about 50 Farad/g to about 500Farad/g, about 100 Farad/g to about 500 Farad/g, about 200 Farad/g toabout 500 Farad/g, about 300 Farad/g to about 500 Farad/g, or about 400Farad/g to about 500 Farad/g.

In some embodiments, the device may store about 50 kJ/kg, about 100kJ/kg, about 200 kJ/kg, about 300 kJ/kg, about 400 kJ/kg, about 500kJ/kg, about 600 kJ/kg, of electrical energy. In some cases, the devicemay store between about 50 kJ/kg and about 600 kJ/kg of electricalenergy.

In some cases, the device is charged to about 1.5 V, about 2.0 V, about2.5 V (e.g., about 2.7 V), about 3.0 V, or, about 3.5 V.

Devices and methods disclosed herein may capable of achieve relativelyhigh specific energy density. In some embodiments, the device mayachieve specific energy densities beyond those which are produced bydevices limited by thermodynamic reduction/oxidation potentials, such asbatteries (e.g., lithium-containing or lithium ion-containingbatteries). Devices and methods disclosed herein can supply individualcell voltages that exceed the thermodynamic limits that would result inbatteries made from the similar materials. In some embodiments, thedevice has a specific energy density of about 100 kJ/kg, about 200kJ/kg, about 300 kJ/kg, about 400 kJ/kg, about 500 kJ/kg, or about 600kJ/kg, based on the total weight of conductive material and, if present,polyacetylene-containing materials within the electrodes. For example,in embodiments where an electrode includes a composite materialcomprising a polymer comprising a substituted or unsubstitutedpolyacetylene and a conductive material, the specific energy density isbased on the total weight of the conductive material and the polymercomprising the substituted or unsubstituted polyacetylene.

At least some of the devices disclosed herein provide an energy storagemechanism that includes both (1) electrostatic storage of electricalenergy achieved by separation of charge in a Helmholtz double layer atthe surface of a conductor electrode and an electrolytic solutionelectrolyte; and (2) electrochemical storage of electrical energyachieved by redox reactions on the surface of at least one of theelectrodes or by specifically adsorbed ions that results in a reversibleFaradaic charge-transfer on the electrode.

Methods for fabricating the devices described herein are also provided.The method may involve forming a conductive material that includes apolymer comprising a substituted or unsubstituted polyacetylene on thesurface of a substrate, such as a charge collector substrate (e.g.,conducting plate). The method may further involve arranging a separatormaterial in contact with the conductive material. For example, a devicemay be fabricated by forming a first conductive material including apolyacetylene-containing polymer the surface of a first substrate, andarranging a first surface of a separator material in contact with thefirst conductive material. A second, conductive material may then bearranged in contact with a second, opposing side of the separatormaterial, such that the first conductive material is in electrochemicalcommunication with the second conductive material. The separatormaterial may also be arranged to physically separate the first andsecond conductive materials. The method may further involve arranging anelectrolyte in contact with the first and second electrodes. FIGS. 1A-Bshow illustrative embodiments of devices as described herein.

Conductive materials described herein may be formed on a substrate usingvarious methods, including evaporation, direct polymerization, inkjetprinting, casting methods including drop-casting and spin-casting, andthe like. In some cases, the conductive material is in the form of asolid, which is then arranged/assembled on a substrate. For example, theconductive material (e.g., polyacetylene-containing polymer) may be inthe form of a powder and arranged between the substrate and anotherdevice component (e.g., the porous separator material). In other cases,the conductive material is combined with a fluid carrier or solvent toform a solution, dispersion, or suspension, and the conductive materialis formed on the substrate via a casting method (e.g., spin-casting,drop-casting, etc.) or by printing (e.g., inkjet printing). For example,a mixture comprising the polymer comprising the substituted orunsubstituted polyacetylene and a fluid carrier may be provided and thenformed into a film. In some cases, films having a thickness in the rangeof about 0.01 mm to about 1 mm may be formed using such methods. Inother cases, the polyacetylene-containing polymer is directlysynthesized on the substrate. The conductive material may be treated byvarious methods to improve processability, physical and/or mechanicalstability, and/or device performance. In some cases, the conductivematerial may be subjected to application of high pressure prior toformation on a substrate. For example, the conductive material (e.g.,polyacetylene-containing polymer) may be in the form of a powder, whichis then placed into a hydraulic press to form a pellet, film, or othershape. In some cases, the conductive material may be subjected tocrosslinking conditions and/or solvent treatments.

As described herein, the device may include a polyacetylene-containingpolymer. In some cases, the devices includes a substituted or anunsubstituted polyacetylene. In some cases, the devices includes acopolymer comprising polyacetylene. The polymer backbone may include cisdouble bonds, trans double bonds, or combinations thereof. In someembodiments, the polymer may include the structure,

wherein:

R¹, R², R³, and R⁴ can be the same or different and each is H, alkyl,heteroalkyl, aryl, heteroaryl, heterocyclyl, halo, cyano, sulfonyl,sulfate, phosphonyl, phosphate, or carbonyl group (e.g., carboxylate,ketones such as alkylcarbonyl or arylcarbonyl, etc.), any of which isoptionally substituted; and

m and n are each greater than 1.

In some embodiments, R¹, R², R³, and R⁴ are each H. In some embodiments,at least one of R¹, R², R³, and R⁴ is halo (e.g., fluorine).

In some embodiments, the polymer has the structure,

wherein m and n are greater than 1.

In some embodiments, the polymer has the structure,

wherein:

R¹, R², R³, and R⁴ can be the same or different and each is H, alkyl,aryl, halo, cyano, sulfonyl, sulfate, phosphonyl, phosphate, or carbonylgroup (e.g., carboxylate, ketones such as alkylcarbonyl or arylcarbonyl,etc.), any of which is optionally substituted; and

m, m′, n, and n′ are each greater than 1.

In some embodiments, the polymer has the structure,

wherein:

R¹, R², R³, and R⁴ can be the same or different and each is H, alkyl,aryl, halo, cyano, sulfonyl, sulfate, phosphonyl, phosphate, or carbonylgroup (e.g., carboxylate, ketones such as alkylcarbonyl or arylcarbonyl,etc.), any of which is optionally substituted; and

m, m′, n, n′, and o are each greater than 1.

In any of the embodiments disclosed herein, n, n′, m, m′ and o are thesame or different and are an integer between 2 and 10,000, or between 10and 10,000, or between 100 and 10,000, or between 100 and 1,000. Themolecular weight of the polyacetylene-containing polymer may be betweenabout 500 and about 1,000,000, or between about 500 and about 100,000,or between about 10,000 and about 100,000, or the like.

Methods described herein may involve the synthesis of polymers includinga substituted or unsubstituted polyacetylene. In some cases, thepolymers may be synthesized in the presence of a fluid carrier, such astoluene. For example, the polymer may be produced using cationicmethods, metal catalyzed insertion reactions, or metal alkylidenereactions proceeding through metallocyclobutene intermediates (alsoknown as a ring opening metathesis polymerization if the acetylene isconsidered to be a two-membered cyclic alkene), and the like. Typically,monomeric species, or a combination of monomeric species, are exposed toa catalyst or catalyst mixture under appropriate conditions in areaction vessel to produce the polymer. In some cases, the monomericspecies includes a carbon-carbon triple bond. In some cases, themonomeric species includes a carbon-carbon double bond. In some cases,the monomeric species includes a carbonyl or C═O group. The monomericspecies may be in vapor phase or in solution phase, and may optionallybe combined with a fluid carrier or solvent (e.g., organic solvent) inthe reaction vessel. In an illustrative embodiment, acetylene gas may beintroduced to the reaction vessel containing a catalyst or catalystmixture. In some cases, the polymer may be synthesized in a gel form,i.e., swollen with solvent and/or other additives. In some cases, thepolymer (e.g., polyacetylene) may be synthesized directly onto asubstrate, e.g., as a film.

In some cases, the method involves polymerizing at least one monomericspecies including a carbon-carbon triple bond to form apolyacetylene-containing polymer. The carbon-carbon triple bond may beunsubstituted (e.g., acetylene) or substituted with one or moresubstituents. In some cases, the monomeric species may be polymerized inthe presence of additional monomers (e.g., to form a copolymer).Examples of additional monomeric species include carbon monoxide, carbondisulfide, and the like. In one set of embodiments, a monomeric speciesincluding a carbon-carbon triple bond and carbon monoxide arecopolymerized to form a polymer including alpha, beta-unsaturatedcarbonyl moieties.

Those of ordinary skill in the art would be able to select a catalyst orcatalyst mixture suitable for use in the synthesis of polymers describedherein. The catalyst may be in solid form (e.g., particles), or combinedwith a solvent to form a solution, suspension, or dispersion. In somecases, the catalyst is a metal-containing catalyst or catalyst mixture.For example, the catalyst or catalyst mixture may include aluminum,titanium, tungsten, ruthenium, rhodium, molybdenum, or combinationsthereof. In some cases, the catalyst may be a mixture including titaniumand aluminum (e.g., Ziegler-Natta catalyst). In some embodiments, thecatalyst or catalyst mixture may comprise ruthenium, rhodium, tungsten,or molybdenum. Examples of catalyst and catalyst mixtures include, butare not limited to, the Ziegler-Natta catalyst (e.g., prepare from,benzylidene-bis(tricyclohexylphosphine)dichloro-ruthenium (Grubbs' firstgeneration catalyst),benzylidene[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro-(tricyclohexylphosphine)ruthenium(Grubbs' second generation catalyst), and Schrock catalysts (e.g.,tris(t-butoxy)(2,2-dimethylpropylidyne)(VI)tungsten).

In some cases, the catalyst or catalyst mixture is in the form ofparticles. For example, the particles may be aerosol-generated catalystparticles.

In some cases, polymers as described here may be produced as highlycrystalline polymers. In some cases, the polymers may form a solid statestructure that is substantially fixed.

The polymerization step may be performed in the presence of additionalcomponents. For example, monomeric species may be polymerized in thepresence of an additive, such that the additive is entrapped ordispersed throughout the resulting polymer material. Such additives maybe selected to be electroactive materials (e.g., polymers) that canenhance performance of the device, e.g., enhance charging, discharging,and/or stabilization of a charged state.

In some cases, the additive may be a passive material that can beremoved post-polymerization. For example, monomeric species may bepolymerized in the presence of an additive, wherein at least some of theadditive is removed post-polymerization to produce a porous polymermaterial. In some cases, the additive may be removed by treatment withheat. In some cases, the additive may be removed by treatment with asolvent.

For example, the polymerization may be performed in the presence of aphase-separating polymer that can be removed after polymerization toyield a porous material. Without wishing to be bound by any theory,since the capacitance of the device may be proportional to the surfacearea of the interface between an electrode and electrolyte, increasingthe surface area of the interface can increase the amount of energystored in the device.

Other examples of additives that may be used during polymerizationinclude other polymers and/or modifiers, such as polydimethylsiloxane,polystyrene, polyethylene, polypropylene, silicone oil, mineral oil,paraffin, cellulosic polymers, polybutadiene, polyneopropene, naturalrubber, or polyimide.

Those of ordinary skill in the art would be able to select a set ofconditions appropriate for a particular polymerization reaction. Forexample, the conditions may be selected based on the chemicalstructure(s) of the monomeric species (e.g., selection of catalyst,solvents, etc.), the stability of the catalyst in the presence of airand/or water, and/or the compatibility (e.g., solubility) of variousreaction components with one another. Exemplary methods for synthesizingpolymers which include a substituted or unsubstituted polyacetylene aredescribed in, for example, Liu et al., “Acetylenic Polymers: Syntheses,Structure, and Functions,” Chem. Rev. 2009, 109, 5799; MacInnes et al.,“Organic Batteries: Reversible n- and p-Type Electrochemical Doping ofPolyacetylene, (CH)_(x),” J.C.S. Chem. Comm. 1981, 371; and Ito et al.,“Simultaneous Polymerization and Formation of Polyacetylene Film on theSurface of Concentrated Soluble Ziegler-Type Catalyst Solution,” J.Polymer Science 1974, 12, 11, the contents of which documents areincorporated herein by reference in their entirety for all purposes.

The polyacetylene-containing polymer may be treated before and/or afterfabrication of the electrodes, or prior to, during, or after thepolymerization step, to improve the performance, stability, and/or otherproperty of the device. In some cases, the polymer may be treated toenhance the charge storage ability of the device. In some cases, thepolymer may be treated to stabilize the polymer material. Suchtreatments may include treatment with dichloroketene (Cl₂C═C═O),aromatic diazonium salts (Ar—N²⁺), disulfides (R—S—S—R), organic sulfurchlorides (RS—Cl), sulfur chlorides (SCl₂ and S₂Cl₂), metal salts andoxides including MnO₂ or Mn(OAc)₂, silicon hydrides (e.g., R_(n)SH₄where R can be alkyl, aryl, vinyl, alkoxy, phenoxy, carboxylate andn=0-4) and disilanes, compounds having one or more silicon hydride group(e.g., SiH) including oligomers and cyclic compounds, polymerscontaining silicon hydrides such as copolymers withpolydimethylsiloxane, phenols including sterically hindered phenols(e.g., butylated hydroxyl toluene (BHT) and derivatives thereof), andother radical scavengers. For example, the polymerization step may beperformed in the presence of a stabilizing agent, such that thatstabilizing agent is dispersed throughout the resulting polymermaterial.

Methods described herein may allow for simplified methods formanufacturing materials and devices including polyacetylene-containingpolymers. In some embodiments, a continuous method for the formation ofthe polyacetylene-containing particles, films, or other materials may beprovided. The continuous process may involve polymerization of a monomerdissolved in a condensed phase (e.g., solution phase) or directpolymerization of a vapor-phase monomer.

For example, the method may involve continuously moving a plurality ofsubstrates through various reaction zones to form apolyacetylene-containing material. In some cases, a substrate may bepassed through a first reaction zone, wherein a catalyst material (e.g.,catalyst particles) may be formed on the substrate. The substratecontaining the catalyst material may then pass through a second reactionzone containing a monomeric species (e.g., acetylene gas), whereinpolymerization takes place at the surface of the substrate on thecatalyst material. Such methods may allow for the production of largequantities of polyacetylene-containing materials and/or formation ofpolyacetylene-containing materials on relatively large surface areas.

The substrate can be any material capable of supporting an electrode andelectrolyte, as described herein. The substrate may be selected to havea thermal coefficient of expansion similar to those of the othercomponents of the device to promote adhesion and prevent separation ofthe components at various temperatures. In some cases, the substrate mayinclude materials capable of facilitating the separation of chargewithin, for example, a double-layer capacitor, i.e., the substrate mayfunction as a charge collector. Examples of substrates include metal(e.g., aluminum) or metal-containing substrates, polymer substrates, andcarbon-based (e.g., carbon, glassy carbon, activated carbon, graphene,graphite, carbon nanotubes, etc.) substrates. The dimensions of thesubstrate may be any length, width, and thickness that is desired for aparticular end use and may be square, rectangular, circular, orotherwise shaped.

Various fluid carriers or solvents may be suitable for use inembodiments described herein. In some cases, the fluid carrier may be anorganic solvent. In some cases, the fluid carrier may be an aqueoussolvent. Examples of fluid carriers and solvents include, but are notlimited to, water, chloroform, carbon dioxide, toluene, benzene, hexane,dichloromethane, tetrahydrofuran, ethanol, acetone, or acetonitrile.

The term “polymers,” as used herein, is given its ordinary meaning inthe art and refers to extended molecular structures comprising abackbone (e.g., non-conjugated backbone, conjugated backbone) whichoptionally contain pendant side groups, where “backbone” refers to thelongest continuous bond pathway of the polymer. Polymers may alsoinclude oligomers. In some embodiments, the polymer comprises anon-conjugated polymer backbone. In some embodiments, at least a portionof the polymer is conjugated, i.e. the polymer has at least one portionalong which electron density or electronic charge can be conducted,where the electronic charge is referred to as being “delocalized.” Insome cases, the polymer is a pi-conjugated polymer, where p-orbitalsparticipating in conjugation can have sufficient overlap with adjacentconjugated p-orbitals. In some cases, the polymer is a sigma-conjugatedpolymer. In one embodiment, at least a portion of the backbone isconjugated. In one embodiment, the entire backbone is conjugated and thepolymer is referred to as a “conjugated polymer.” Polymers having aconjugated pi-backbone capable of conducting electronic charge may alsobe referred to as “conducting polymers.” In some cases, the conjugatedpi-backbone may be defined by a plane of atoms directly participating inthe conjugation, wherein the plane arises from a preferred arrangementof the p-orbitals to maximize p-orbital overlap, thus maximizingconjugation and electronic conduction.

As used herein, the term “alkyl” refers to the radical of saturatedaliphatic groups, including straight-chain alkyl groups, branched-chainalkyl groups, cycloalkyl (alicyclic) groups, alkyl substitutedcycloalkyl groups, and cycloalkyl substituted alkyl groups. In someembodiments, a straight chain or branched chain alkyl may have 30 orfewer carbon atoms in its backbone, and, in some cases, 20 or fewer. Insome embodiments, a straight chain or branched chain alkyl has 12 orfewer carbon atoms in its backbone (e.g., C₁-C₁₂ for straight chain,C₃-C₁₂ for branched chain), or, in some cases, 6 or fewer, or 4 orfewer. Likewise, some cycloalkyls have from 3-10 carbon atoms in theirring structure, or have 5, 6 or 7 carbons in the ring structure.Examples of alkyl groups include, but are not limited to, methyl, ethyl,propyl, isopropyl, cyclopropyl, butyl, isobutyl, tert-butyl, cyclobutyl,hexyl, cyclohexyl, and the like.

The term “heteroalkyl” refers to an alkyl group as described herein inwhich one or more carbon atoms is replaced by a heteroatom. Suitableheteroatoms include oxygen, sulfur, nitrogen, phosphorus, and the like.Examples of heteroalkyl groups include, but are not limited to, alkoxy,amino, thioester, and the like.

The term “aryl” refers to aromatic carbocyclic groups, optionallysubstituted, having a single ring (e.g., phenyl), multiple rings (e.g.,biphenyl), or multiple fused rings in which at least one is aromatic(e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl).That is, at least one ring may have a conjugated pi electron system,while other, adjoining rings can be cycloalkyls, cycloalkenyls,cycloalkynyls, aryls and/or heterocyclyls. The aryl group may beoptionally substituted, as described herein. “Carbocyclic aryl groups”refer to aryl groups wherein the ring atoms on the aromatic ring arecarbon atoms. Carbocyclic aryl groups include monocyclic carbocyclicaryl groups and polycyclic or fused compounds (e.g., two or moreadjacent ring atoms are common to two adjoining rings) such as naphthylgroups.

The term “heteroaryl” refers to aryl groups comprising at least oneheteroatom as a ring atom.

The term “heterocyclyl” refers to refer to cyclic groups containing atleast one heteroatom as a ring atom, in some cases, 1 to 3 heteroatomsas ring atoms, with the remainder of the ring atoms being carbon atoms.Suitable heteroatoms include oxygen, sulfur, nitrogen, phosphorus, andthe like. In some cases, the heterocycle may be 3- to 10-membered ringstructures, or in some cases 3- to 7-membered rings, whose ringstructures include one to four heteroatoms. The term “heterocycle” mayinclude heteroaryl groups (e.g., aromatic heterocycles), saturatedheterocycles (e.g., cycloheteroalkyl) groups, or combinations thereof.The heterocycle may be a saturated molecule, or may comprise one or moredouble bonds. In some case, the heterocycle is an aromatic heterocycle,such as pyrrole, pyridine, and the like. In some cases, the heterocyclemay be attached to, or fused to, additional rings to form a polycyclicgroup. In some cases, the heterocycle may be part of a macrocycle. Theheterocycle may also be fused to a spirocyclic group. In some cases, theheterocycle may be attached to a compound via a nitrogen or a carbonatom in the ring.

Heterocycles include, for example, thiophene, benzothiophene,thianthrene, furan, tetrahydrofuran, pyran, isobenzofuran, chromene,xanthene, phenoxathiin, pyrrole, dihydropyrrole, pyrrolidine, imidazole,pyrazole, pyrazine, isothiazole, isoxazole, pyridine, pyrazine,pyrimidine, pyridazine, indolizine, isoindole, indole, indazole, purine,quinolizine, isoquinoline, quinoline, phthalazine, naphthyridine,quinoxaline, quinazoline, cinnoline, pteridine, carbazole, carboline,triazole, tetrazole, oxazole, isoxazole, thiazole, isothiazole,phenanthridine, acridine, pyrimidine, phenanthroline, phenazine,phenarsazine, phenothiazine, furazan, phenoxazine, pyrrolidine, oxolane,thiolane, oxazole, oxazine, piperidine, homopiperidine(hexamnethyleneimine), piperazine (e.g., N-methyl piperazine),morpholine, lactones, lactams such as azetidinones and pyrrolidinones,sultams, sultones, other saturated and/or unsaturated derivativesthereof, and the like. The heterocyclic ring can be optionallysubstituted at one or more positions with such substituents as describedherein. In some cases, the heterocycle may be bonded to a compound via aheteroatom ring atom (e.g., nitrogen). In some cases, the heterocyclemay be bonded to a compound via a carbon ring atom. In some cases, theheterocycle is pyridine, imidazole, pyrazine, pyrimidine, pyridazine,acridine, acridin-9-amine, bipyridine, naphthyridine, quinoline,benzoquinoline, benzoisoquinoline, phenanthridine-1,9-diamine, or thelike.

As used herein, the term “halo” designates —F, —Cl, —Br, or —I.

The terms “carboxyl group,” “carbonyl group,” and “acyl group” arerecognized in the art and can include such moieties as can berepresented by the general formula:

wherein W is H, OH, O-alkyl, O-alkenyl, or a salt thereof. Where W isO-alkyl, the formula represents an “ester.” Where W is OH, the formularepresents a “carboxylic acid.” The term “carboxylate” refers to ananionic carboxyl group. In general, where the oxygen atom of the aboveformula is replaced by sulfur, the formula represents a “thiolcarbonyl”group. Where W is a S-alkyl, the formula represents a “thiolester.”Where W is SH, the formula represents a “thiolcarboxylic acid.” On theother hand, where W is alkyl or aryl, the above formula represents a“ketone” group (e.g., alkylcarbonyl, arylcarbonyl, etc.). Where W ishydrogen, the above formula represents an “aldehyde” group.

Any of the above groups may be optionally substituted. As used herein,the term “substituted” is contemplated to include all permissiblesubstituents of organic compounds, “permissible” being in the context ofthe chemical rules of valence known to those of ordinary skill in theart. It will be understood that “substituted” also includes that thesubstitution results in a stable compound, e.g., which does notspontaneously undergo transformation such as by rearrangement,cyclization, elimination, etc. In some cases, “substituted” maygenerally refer to replacement of a hydrogen with a substituent asdescribed herein. However, “substituted,” as used herein, does notencompass replacement and/or alteration of a key functional group bywhich a molecule is identified, e.g., such that the “substituted”functional group becomes, through substitution, a different functionalgroup. For example, a “substituted phenyl group” must still comprise thephenyl moiety and cannot be modified by substitution, in thisdefinition, to become, e.g., a pyridine ring. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described herein. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this invention, the heteroatoms such as nitrogen mayhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valencies of theheteroatoms.

Examples of substituents include, but are not limited to, halogen,azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl,amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate,carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido,ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromaticmoieties, —CF₃, —CN, aryl, aryloxy, perhaloalkoxy, aralkoxy, heteroaryl,heteroaryloxy, heteroarylalkyl, heteroaralkoxy, azido, amino, halide,alkylthio, oxo, acylalkyl, carboxy esters, -carboxamido, acyloxy,aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl,arylamino, aralkylamino, alkylsulfonyl, -carboxamidoalkylaryl,-carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy-,aminocarboxamidoalkyl-, cyano, alkoxyalkyl, perhaloalkyl,arylalkyloxyalkyl, and the like.

EXAMPLES AND EMBODIMENTS Example 1

The following example describes the preparation of a polyacetylenepolymer. To a 100 mL Schlenk flask purged with dry nitrogen was addeddry toluene (30 mL), followed by tetrabutoxytitanium (5.2 g, 15 mmol).Triethylaluminum solution in toluene (31 mL, 1.9 M, 60 mmoL) was slowlyadded, and the resulting mixture was stirred for 4 h at room temperatureto form the catalyst solution, which was stored under nitrogen.

In a separate flask was added dry toluene (40 mL) and small amount ofthe catalyst solution (0.6 mL). Acetylene gas, which was purified bypassing through a dry ice trap, was introduced via a syringe needle. Thepolymerization was allowed to continue for 16 h. The polymer wassuspended in isopropanol, and the precipitates were collected byfiltration, washed with isopropanol, and dried under vacuum to yieldpolyacetylene (3.4 g).

Example 2

In the following example, a supercapacitor device was assembledaccording to FIG. 1B. The negative electrode was Spectracarb ActivatedCarbon Fabric Type 2225 from Engineered Fibers Technology, LLC. In arepresentative experiment, polyacetylene (5.9 mg) was ground into fineparticles and evenly spread on the surface of half of the 2.5×2.5 cm²glassy carbon, and the polyacetylene was then completely covered with apiece of filter paper (Whatman #6). On top of the filter paper wasplaced the carbon cloth cut into rectangular shape, just enough to coverthe polyacetylene area (the weight of the carbon cloth was 50 mg). Ontop of the carbon cloth was placed another 2.5×2.5 cm² glassy carbonsquare. The completed assembly was then clamped together with bindclips, and electrolyte (prepared by mixing tetraethyammoniumhexafluorophosphate, propylene carbonate, and ethylene carbonate in aweight ratio of 2:1:1) was then added through the edge of the device.

Example 3

The following example describes the performance of the supercapacitordevice described in Example 2. The device was analyzed by charging atconstant current (0.002 A) until the voltage reached 2.7 V, and thendischarging at constant current (0.002 A) until the voltage reached 0.The device voltage was monitored continuously every microsecond duringthe charging discharging process. The charging/discharging process wasrepeated three times. FIG. 3 shows the voltage charging staterelationship during the first three cycles. The capacitance of thedevice was estimated as 1.53 by calculating the reciprocal of the linepassing the both ends of the curve. (FIG. 4) The specific capacitancebased on polyacetylene was calculated to be 259 kF/kg. The specificenergy based on polyacetylene was calculated by integrate the energyreleased during the first discharging (FIG. 5, the total energy releasedduring the first discharging was 5.2 J) and dividing the total by themass of the polyacetylene. The calculated specific energy density was882 kJ/kg.

Example 4

In the following example, various electrode materials were prepared.

In one exemplary procedure, polyacetylene films were prepared using abinder such as polytetrafluoroethylene (PTFE). In a representativeprocedure, polyacetylene (1 g) was ground into fine powder and mixedwith polytetrafluoroethylene (PTFE, 60% suspension in water, 0.167 g),and further diluted with water (2 g). The resulting dough-like materialwas rolled into 200 micron film on a rolling mill. The resulting filmwas then dried under vacuum and cut into desirable sizes to be used aspositive electrodes in supercapacitor devices.

In another exemplary procedure, polyacetylene films using hydraulicpress, without addition of any binders. In a representative procedure,polyacetylene (4 g) was ground into fine powder, and was evenly loadedonto a 5×5 cm² square shaped press die. 12 Tons of force was applied toresult in a 5×5 cm² polyacetylene film, which was then cut intodesirable sizes to be used as electrodes in supercapacitor devices.

In another exemplary procedure, activated carbon films were preparedusing polytetrafluoroethylene (PTFE) as binder. In a representativeprocedure, activated carbon (2.0 g) was mixed withpolytetrafluoroethylene (PTFE, 60% suspension in water, 0.5 g) and water(4.5 mL). The resulting mixture was kneaded into a dough-like materialand rolled into 200 micron film on a rolling mill. The film was then cutinto desirable sizes to be used as electrodes in supercapacitor devices.

Example 5

In the following example, single-cell capacitors were prepared usingpolyacetylene films as positive electrodes. The films were prepared witha polytetrafluoroethylene (PTFE) binder, according to the proceduredescribed in Example 4.

A polyacetylene film (168.2 mg), activated carbon film (213.4 mg), andcellulose separator, all saturated with electrolyte(1-Ethyl-3-methylimidazolium tetrafluoroborate), were assembled withaluminum foil as shown in FIG. 6. The interfaces between aluminumfoil/polyacetylene film and aluminum foil/activated carbon film weredusted with activated carbon powder (6.9 mg and 5.1 mg respectively) toenhance conductivity. The completed assembly was then pressed betweentwo glass slides held together by binder clip.

The performance of this device was tested by passing a constant currentinto polyacetylene film from the activated carbon film, until thepotential difference between the two electrodes reached 3.5 V, and thenthe direction of the current was reversed. The energy density of thecompleted device based on energy released during first cycle was 65kJ/kg (245 kJ/kg based on the total weight of carbon and polyacetylenematerials on the electrodes).

Example 6

In the following example, single-cell capacitors were prepared usingpressed polyacetylene films as positive electrodes. The films wereprepared with a polytetrafluoroethylene (PTFE) binder, according to theprocedure described in Example 4. A polytetrafluoroethylene film, binder(198.0 mg), activated carbon film (217.5 mg), and cellulose separator,all saturated with electrolyte (1-ethyl-3-methylimidazoliumtetrafluoroborate), were assembled with aluminum foil according to FIG.6. The interfaces between aluminum foil/polyacetylene film and aluminumfoil/activated carbon film were dusted with activated carbon powder(10.3 mg and 10.2 mg respectively) to enhance conductivity. Thecompleted assembly was then pressed between two glass slides heldtogether by binder clip.

The performance of this device was tested by passing a constant currentinto polyacetylene film from the activated carbon film, until thepotential difference between the two electrodes reached 3.5 V, and thenthe direction of the current was reversed. The energy density of thecompleted device based on energy released during first cycle was 81kJ/kg (256 kJ/kg based on the total weight of carbon and polyacetylenematerials on the electrodes).

Example 7

In the following example, multi-cell capacitors were prepared usingpolyacetylene films as positive electrodes. Three polyacetylene films(220.2 mg, 227.3 mg, and 216.8 mg), three activated carbon films (219.9mg, 249.5 mg, 297.4 mg), and cellulose separators, all saturated withelectrolyte (1-ethyl-3-methylimidazolium tetrafluoroborate), wereassembled with aluminum foils according to FIG. 7. The interfacesbetween aluminum foil/polyacetylene film and aluminum foil/activatedcarbon film were dusted with activated carbon powder (9.9-11.2 mg) toenhance conductivity. The completed assembly was then pressed betweentwo glass slides held together by binder clip.

The performance of this device was tested by passing a constant currentinto polyacetylene film from the activated carbon film, until thepotential difference between the two electrodes reached 3.5 V, and thenthe direction of the current was reversed. The energy density of thecompleted device based on energy released during first cycle was 60kJ/kg (242 kJ/kg based on the total weight of carbon and polyacetylenematerials on the electrodes).

Having thus described several aspects of some embodiments, it is to beappreciated various alterations, modifications, and improvements willreadily occur to those skilled in the art. Such alterations,modifications, and improvements are intended to be part of thisdisclosure, and are intended to be within the spirit and scope of theinvention. Accordingly, the foregoing description and drawings are byway of example only.

What is claimed:
 1. An electrical energy storage device, comprising: afirst electrode comprising a polymer comprising a substituted orunsubstituted polyacetylene; a second electrode in electrochemicalcommunication with the first electrode; a porous separator materialarranged between the first and second electrodes; and an electrolyte inelectrochemical communication with the first and second electrodes,wherein the electrolyte is a substantially free of lithium-containingspecies or lithium ion-containing species.
 2. An electrical energystorage device as in claim 1, wherein the electrolyte is a substantiallyfree of metal-containing species.
 3. An electrical energy storage deviceas in claim 1, wherein the polymer comprising the substituted orunsubstituted polyacetylene is synthesized in the presence of a fluidcarrier.
 4. An electrical energy storage device as in claim 1, whereinthe electrolyte is an ethylene carbonate solution or a propylenecarbonate solution, the solution comprising a salt having the formula,[(R)₄N⁺][X⁻], wherein X is (PF₆)⁻, (BF₄)⁻, (SO₃R^(a))⁻,(R^(a)SO₂—N—SO₂R^(a))⁻, CF₃CO₂ ⁻, (CF₃)₃CO⁻, or (CF₃)₂CHO)⁻, wherein Ris alkyl and R^(a) is alkyl, aryl, fluorinated alkyl, or fluorinatedaryl.
 5. An electrical energy storage device as in claim 1, wherein thesubstituted or unsubstituted polyacetylene polymer is arranged as ann-type material.
 6. An electrical energy storage device as in claim 1,wherein the substituted or unsubstituted polyacetylene polymer isarranged as a p-type material.
 7. An electrical energy storage device asin claim 1, wherein the polymer comprises the structure,

wherein: R¹, R², R³, and R⁴ can be the same or different and each is H,alkyl, heteroalkyl, aryl, heteroaryl, heterocyclyl, halo, cyano,sulfonyl, sulfate, phosphonyl, phosphate, or carbonyl group, any ofwhich is optionally substituted; and m and n are each greater than
 1. 8.An electrical energy storage device as in claim 7, wherein R¹, R², R³,and R⁴ are each H.
 9. An electrical energy storage device as in claim 7,wherein at least one of R¹, R², R³, and R⁴ is fluorine.
 10. Anelectrical energy storage device as in claim 1, wherein the polymer hasthe structure,

wherein m and n are greater than
 1. 11. An electrical energy storagedevice as in claim 1, wherein the polymer has the structure,

wherein: R¹, R², R³, and R⁴ can be the same or different and each is H,alkyl, aryl, halo, cyano, sulfonyl, sulfate, phosphonyl, phosphate, orcarbonyl group, any of which is optionally substituted; and m, m′, n,and n′ are each greater than
 1. 12. An electrical energy storage deviceas in claim 1, wherein the polymer has the structure,

wherein: R¹, R², R³, and R⁴ can be the same or different and each is H,alkyl, aryl, halo, cyano, sulfonyl, sulfate, phosphonyl, phosphate, orcarbonyl group, any of which is optionally substituted; and m, m′, n,n′, and o are each greater than
 1. 13. An electrical energy storagedevice as in claim 12, wherein n, n′, m, m′ and o are the same ordifferent and are an integer between about 2 and about 10,000, orbetween about 10 and about 10,000, or between about 100 and about10,000, or between about 100 and about 1,000r.
 14. An electrical energystorage device as in claim 1, wherein the polymer has a molecular weightbetween about 500 and about 1,000,000, or between about 500 and about100,000, or between about 10,000 and about 100,000.
 15. An electricalenergy storage device as in claim 1, wherein the porous separatormaterial is paper.
 16. An electrical energy storage device as in claim1, wherein the porous separator material comprises a polymer.
 17. Anelectrical energy storage device as in claim 1, wherein the porousseparator material comprises polypropylene, polyethylene, cellulose, apolyarylether, or a fluoropolymer.
 18. An electrical energy storagedevice as in claim 1, wherein the polymer comprising a substituted orunsubstituted polyacetylene is provided in a blend with at least onepolymer that is different than the polymer comprising a substituted orunsubstituted polyacetylene.
 19. An electrical energy storage device asin claim 1, wherein the polymer comprising a substituted orunsubstituted polyacetylene is provided in a blend with at least oneconducting polymer.
 20. An electrical energy storage device as in claim19, wherein the at least one conducting polymer is a derivative ofpolyaniline, polyphenylene, polyarylene, poly(bisthiophene phenylene), aladder polymer, poly(arylene vinylene), or poly(arylene ethynylene), anyof which is optionally substituted.
 21. An electrical energy storagedevice as in claim 19, wherein the conducting polymer is an optionallysubstituted polythiophene or polymer containing thiophene units that areconnected by aromatic groups or alkenes.
 22. An electrical energystorage device as in claim 19, wherein the conducting polymer is anoptionally substituted polypyrrole or polymer containing pyrrole unitsthat are connected by aromatic groups or alkenes.
 23. An electricalenergy storage device, comprising: a first electrode comprising apolymer comprising a substituted or unsubstituted polyacetylene; asecond electrode in electrochemical communication with the firstelectrode; a porous separator material arranged between the first andsecond electrodes; and an electrolyte in electrochemical communicationwith the first and second electrodes, wherein the electrolyte is anethylene carbonate solution or a propylene carbonate solution, thesolution comprising a salt having the formula, [(R)₄N⁺][X⁻], wherein Xis (PF₆)⁻, (BF₄)⁻, (SO₃R^(a))⁻, (R^(a)SO₂—N—SO₂R^(a))⁻, CF₃CO₂,(CF₃)₃CO⁻, or (CF₃)₂CHO)⁻, wherein R is alkyl and R^(a) is alkyl, aryl,fluorinated alkyl, or fluorinated aryl.